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WO2013000892A1 - Article fabriqué par moulage par injection - Google Patents

Article fabriqué par moulage par injection Download PDF

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Publication number
WO2013000892A1
WO2013000892A1 PCT/EP2012/062321 EP2012062321W WO2013000892A1 WO 2013000892 A1 WO2013000892 A1 WO 2013000892A1 EP 2012062321 W EP2012062321 W EP 2012062321W WO 2013000892 A1 WO2013000892 A1 WO 2013000892A1
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Prior art keywords
components
acid
mol
weight
total weight
Prior art date
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Ceased
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PCT/EP2012/062321
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German (de)
English (en)
Inventor
Kai Oliver Siegenthaler
Jörg AUFFERMANN
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BASF SE
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BASF SE
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Application filed by BASF SE filed Critical BASF SE
Priority to ES12729630.9T priority Critical patent/ES2552948T3/es
Priority to EP12729630.9A priority patent/EP2726549B1/fr
Priority to BR112013032053A priority patent/BR112013032053B1/pt
Priority to CN201280031946.3A priority patent/CN103635533B/zh
Publication of WO2013000892A1 publication Critical patent/WO2013000892A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the present invention relates to an injection molded article comprising: i) from 50 to 85% by weight, based on the total weight of components i to ii, of a biodegradable polyester having an MVR (190 ° C, 2.16 kg) ISO 1133 of 10 to 100 cm 3/10 min comprising:
  • 1,4-butanediol d) 0 to 0.1% by weight, based on the components a to c of a chain extender or branching agent; ii) from 15 to 50% by weight, based on the total weight of components i to ii, of polylactic acid; iii) from 10 to 50% by weight, based on the total weight of components i to iv, of at least one or more mineral fillers, at least one filler being chalk; iv) 0 to 2 wt .-%, based on the total weight of components i to iv, of a nutrient salt mixture containing at least two components selected from the group consisting of: nitrogen-containing cation or anion, sulfur-containing anion, phosphorus-containing anion and Cation selected from the group consisting of K + , Na + , Ca 2+ , Mg 2+ and Fe 2/3 + .
  • the invention relates to methods for producing the above-mentioned articles.
  • Filled biodegradable polymer blends containing a soft polymer such as an aliphatic-aromatic polyester (PBAT) and a rigid polymer such as polylactic acid (PLA) are known from US 6,573,340 and WO 2005/063883. Injection molded articles produced therefrom, however, can not always fully convince in terms of heat distortion resistance, stress-strain behavior (elastic modulus) and biodegradability. From DE 198 57 067 monofilaments are known which contain polybutylene succinate (PBS), polylactic acid and talc. The polymer mixtures mentioned have too low biodegradability for many injection molding applications. The aim of the present invention was thus to provide injection-molded articles which do not have the abovementioned disadvantages.
  • PBS polybutylene succinate
  • the goal has been to provide a sufficiently rigid plastic having a heat distortion resistance sufficient for hot food applications.
  • the biodegradability rate should be sufficiently high for an article with wall thicknesses of 50 ⁇ m to 2 mm to be certified to ISO 17088 and / or EN 13432 and / or ASTM D6400.
  • an article produced by injection molding contains: i) 50 to 85% by weight, based on the total weight of components i to ii, of a biodegradable polyester having an MVR (190 ° C., 2.16 kg) according to ISO 1133 of 10 to 100 cm 3/10 min comprising:
  • component i guarantees a high degree of heat resistance and at the same time good biodegradability
  • component ii provides the necessary rigidity and, in addition, improves the biodegradability by means of a supplementary decomposition mechanism.
  • the mineral filler iii) improves the mechanical properties such as modulus of elasticity and heat resistance and promotes such as chalk in particular the biodegradability. The invention will be described in more detail below.
  • polyesters i suitable for the invention are described in more detail in WO 2010/03471 1, to which reference is expressly made here.
  • polyesters i have the following structure: a) from 90 to 99.5 mol%, based on the components a to b, of succinic acid; b) 0.5 to 10 mol%, based on the components a to b, of one or more C8-C20 dicarboxylic acids; c) 98 to 102 mol%, based on the components a to b, 1, 3-propanediol or 1, 4-butanediol and d) 0 to 0.1 wt .-%, based on the total weight of the components a to c, a chain extender or splitter.
  • the synthesis of the described copolyesters preferably takes place in a direct polycondensation reaction of the individual components.
  • the dicarboxylic acid derivatives are reacted together with the diol in the presence of a transesterification catalyst directly to the polycondensate of high molecular weight.
  • the polyester can also be obtained by transesterification of polybutylene succinate (PBS) with C8-C20 dicarboxylic acids in the presence of diol.
  • PBS polybutylene succinate
  • the catalysts used are usually zinc, aluminum and in particular titanium catalysts.
  • Titanium catalysts such as tetra (isopropyl) orthotitanate and in particular tetraisobutoxy titanate (TBOT) have the advantage over the tin, antimony, cobalt and lead catalysts frequently used in the literature, such as, for example, tin dioctanoate, that residual amounts of catalyst or secondary product of the catalyst remaining in the product are less toxic. This fact is particularly important in the case of biodegradable polyesters, since they enter the environment directly, for example as composting bags or mulch films.
  • TBOT tetraisobutoxy titanate
  • a mixture of the dicarboxylic acids is generally heated in the presence of an excess of diol together with the catalyst usually first for a period of about 60-180 min to an internal temperature of 170 to 230 ° C and distilled off any water formed. Subsequently, the melt of the prepolyester thus obtained is usually at an internal temperature of 200 to 250 ° C within 3 to 6 hours at reduced
  • VZ viscosity number
  • the copolymers according to the invention can furthermore be prepared by the processes described in WO 96/15173 and EP-A 488 617. It has proven to be advantageous first to react the components a to c to give a prepolyester having a VZ of 50 to 100 ml / g, preferably 60 to 80 ml / g, and then this with chain extenders d, for example with diisocyanates or with epoxy-containing polymethacrylates a chain extension reaction to a polyester with a VZ of 50 to 450 mL / g, preferably 95 to 200 mL / g implement.
  • Succinic acid is accessible by petrochemical route and preferably from renewable raw materials such as described for example in PCT / EP2008 / 006714.
  • PCT / EP2008 / 006714 discloses a biotechnological process for the production of succinic acid and 1, 4-butanediol from different carbohydrates with microorganisms from the class of Pasteurellaceae.
  • Acid component b is used in 0.5 to 10 mol%, preferably 1 to 9 mol%, and particularly preferably 2 to 8 mol%, based on the acid components a and b.
  • C8-C20 dicarboxylic acids b are to be understood as meaning, in particular, terephthalic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid and / or arachidonic acid. Preference is given to suberic acid, azelaic acid, sebacic acid and / or brassylic acid.
  • the above acids including terephthalic acid are available from renewable resources.
  • sebacic acid is available from castor oil.
  • Such polyesters are characterized by an excellent biological degradation behavior [literature: Polym. Degr. Rod. 2004, 85, 855-863].
  • the dicarboxylic acids a and b can be used either as the free acid or in the form of ester-forming derivatives.
  • ester-forming derivatives are the C 1 -C 1 -alkyl esters, such as dimethyl, diethyl, di-n-propyl, diisopropyl, di-n-butyl, di-iso-butyl, di-t-butyl, Di-n-pentyl, di-iso-pentyl or di-n-hexyl esters.
  • Anhydrides of dicarboxylic acids can also be used.
  • the dicarboxylic acids or their ester-forming derivatives can be used individually or as a mixture.
  • the diols 1, 3-propanediol and 1, 4-butanediol are also available from renewable resources. It is also possible to use mixtures of the two diols. Because of the higher melting temperatures and the better crystallization of the copolymer formed, 1,4-butanediol is preferred as the diol.
  • the diol (component c) is added to the acids (components a and b) in a ratio of diol to diacids of from 1.0 to 2.5: 1 and preferably from 1.3 to 2.2: 1 set. Excess diol are withdrawn during the polymerization, so that sets an approximately equimolar ratio at the end of the polymerization. By approximately equimolar is meant a diol / diacid ratio of 0.90 to 1.10.
  • Chain extenders and alcohols or carboxylic acid derivatives having at least three functional groups can also be understood as crosslinkers.
  • Particularly preferred compounds have three to six functional groups. Examples which may be mentioned are: tartaric acid, citric acid, malic acid, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic dianhydride; Trimethylolpropane, trimethylolethane; Pentaerythritol, polyether triols and glycerin. Preference is given to polyols such as trimethylolpropane, pentaerythritol and in particular glycerol.
  • Components d can be used to build biodegradable polyesters with a structural viscosity.
  • the rheological behavior of the melts improves;
  • the biodegradable polyesters are easier to process, for example, better by melt consolidation to remove films.
  • the compounds d are shear-thinning, i. they increase the intrinsic viscosity of the polymer.
  • the viscosity under load is reduced.
  • Suitable bifunctional chain extenders are, for example, toluylene-2,4-diisocyanate, toluene-2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene-1 , 5-diisocyanate or xylylene diisocyanate, 1, 6
  • the polyesters i generally have a number average molecular weight (Mn) in the range from 8000 to 100,000, in particular in the range from 8000 to 50,000 g / mol, a weight-average molecular weight (Mw) of 10,000 to 300,000, preferably 10,000 to 120,000 g / mol and a Mw / Mn ratio of 1 to 6, preferably 2 to 4.
  • the viscosity number is between 30 and 450, preferably from 50 to 200 g / ml (measured in o-dichlorobenzene / phenol (weight ratio 50/50)).
  • the melting point is in the range of 85 to 130, preferably in the range of 95 to 120 ° C.
  • PLA polylactic acid
  • Polylactic acid having the following property profile is preferably used:
  • melt volume rate (MVR at 190 ° C. and 2.16 kg according to ISO 1 133 from 0.5 to 40, in particular from 15 to 25 ml / 10 minutes)
  • Preferred polylactic acids are, for example, NatureWorks® Ingeo 6201 D, 6202 D, 6251 D, 3051 D and in particular 3051 D or 3251 D and crystalline polylactic acid types from NatureWorks.
  • the polylactic acid ii is used in a percentage by weight, based on the components i and ii, of from 15 to 50%, preferably from 15 to 45% and particularly preferably from 20 to 40%.
  • the polylactic acid ii forms the disperse phase and the polyester i the continuous or is part of a co-continuous phase.
  • Polymer blends with polyester i in the continuous phase or as part of a co-continuous phase have a higher heat resistance than polymer blends in which polylactic acid ii forms the continuous phase.
  • at least one mineral filler selected from the group consisting of: chalk, graphite, gypsum , Conductive carbon black, iron oxide, calcium chloride, dolomite, kaolin, silicon dioxide (quartz), sodium carbonate, titanium dioxide, silicate, wollastonite, mica, montmorillonite, talc and mineral fibers.
  • the chalk is used as filler in the Compounds according to the invention mandatory.
  • the chalk is preferably added in 5 to 35% by weight, preferably 8 to 30% by weight, particularly preferably 10 to 20% by weight, based on the total weight of components i to iv.
  • Talcum in turn can increase the modulus of elasticity more effectively and improve its heat resistance.
  • the combination of chalk and talc is especially preferred as fillers.
  • biodegradable for a substance or a substance mixture is fulfilled if this substance or the substance mixture according to DIN EN 13432 has a percentage degree of biodegradation of at least 90% after 180 days.
  • biodegradability causes the polyester (mixtures) to decompose in a reasonable and detectable time.
  • Degradation can be effected enzymatically, hydrolytically, oxidatively and / or by the action of electromagnetic radiation, for example UV radiation, and mostly for the most part be effected by the action of microorganisms such as bacteria, yeasts, fungi and algae.
  • the biodegradability can be quantified, for example, by mixing polyesters with compost and storing them for a certain period of time. For example, according to DIN EN 13432 (referring to ISO 14855), C02-free air is allowed to flow through matured compost during composting and subjected to a defined temperature program.
  • biodegradability is determined by the ratio of the net CO 2 release of the sample (after subtraction of CO 2 release by the compost without sample) to the maximum CO 2 release of the sample (calculated from the carbon content of the sample) as a percentage of biodegradation Are defined.
  • Biodegradable polyesters (mixtures) usually show clear signs of decomposition after just a few days of composting, such as fungal growth, cracking and hole formation.
  • injection molding which is also referred to as injection molding or injection molding is a molding process that is used very often in plastics processing. In injection molding can be produced very economically direct usable moldings in large quantities. The procedure is simplified as follows: In an injection molding machine consisting of a heatable cylinder in which the worm shaft rotates, the respective thermoplastic material ("molding compound") is melted and injected into a mold made of metal ("tool"). The cavity of the tool determines the shape and the surface chen fabricat of the finished part. Today, parts of well under one gram can be produced in the double-digit kilogram range.
  • Injection molding can produce commodities with high accuracy economically and in a short time.
  • the nature of the surface of the respective component can be chosen almost freely by the designers. From smooth surfaces for optical applications, to grooving for touch-friendly areas, to patterns or engravings, a variety of surface structures can be visualized.
  • the injection molding process is suitable for economic reasons, especially for the production of larger quantities, because only the cost of the injection molding form a significant portion of the necessary investments. And even with simple tools, the purchase pays off only from the production of several thousand parts.
  • polymer mixtures of the components I to IV are suitable with a MVR (190 ° C, 2.16 kg) according to ISO 1133 of 10 to 100 cm 3/10 min, preferably from 10 to 80 cm 3/10 min and particularly preferably from 25 to 60 cm 3/10 min.
  • MVR 190 ° C, 2.16 kg
  • linear or only slightly branched polyesters have proved to be suitable in these polymer blends which contain from 0 to 0.1% by weight, based on the components a to c, of a branching agent.
  • the molecular weights Mn and Mw of the partially aromatic polyesters were determined by SEC according to DIN 55672-1: eluent hexafluoroisopropanol (HFIP) + 0.05% by weight of trifluoroacetic acid Ka salt; The calibration was done with narrow polymethyl methacrylate standards.
  • the determination of the viscosity numbers was carried out according to DIN 53728 Part 3, January 3, 1985, capillary viscosimetry.
  • a micro Ubbelohde viscometer, type M-II was used.
  • the solvent used was the mixture: phenol / o-dichlorobenzene in a weight ratio of 50/50.
  • the modulus of elasticity was determined by means of a tensile test on press foils having a thickness of about 420 ⁇ m in accordance with ISO 527-3: 2003.
  • the Charpy impact strength was determined according to ISO 179-2 / 1 eU: 1997.
  • the specimen (80mm x 10mm x4mm), stored near its ends as a horizontal bar, is stressed by a single impact of a pendulum with the impact line in the middle between the two specimen abutments and (the specimen) with a high , Nominal constant speed (2.9 or 3.8 m / s) is bent.
  • the heat distortion temperature HDT-B was determined according to ISO 75-2: 2004. A standard test piece is subjected to a three-point bend under constant load to produce a bend (HDT / B 0.45 MPa) specified in the relevant part of this International Standard. The temperature is increased at a uniform rate (120 K / h), and the temperature value at which a predetermined standard deflection corresponding to the specified bending elongation increase (0.2%) is reached is measured.
  • the degradation rates of the biodegradable polyester blends and the blends prepared for comparison were determined as follows:
  • films having a thickness of 400 ⁇ m were respectively produced by pressing at 190 ° C. These films were each cut into rectangular pieces with edge lengths of 2 x 5 cm. The weight of these pieces of film was determined. Over a period of four weeks, the pieces of film were heated to 58 ° C in a drying oven in a plastic can filled with humidified compost. At weekly intervals, the remaining weight of the foil pieces was measured in each case.
  • Polyester i a) Polylbutylene succinate (comparative system)
  • butanediol (93.7 g, 130 mol%), succinic acid (94.5 g, 100 mol%) and glycerol 0.2 g (0.1 wt%) in the presence of tetrabutyl ortho-titanate TBOT ( 0.2 g) was heated to 200 ° C and for 30 min, the resulting water was distilled off. This prepolyester was then reacted at reduced pressure ( ⁇ 5 mbar) to high molecular weight polyester. For this purpose, 1, 4-butanediol was distilled off up to a temperature of 250 ° C. The resulting polyester had a VZ of 171 mL / g.
  • Butanediol (85 g, 130 mol%), succinic acid (77.1 g, 90 mol%), brassylic acid (18.1 g, 10 mol%) and glycerol 0.17 g (0.1 wt%) were dissolved in the presence of TBOT ( 0.2 g) is first heated to 200 ° C. The melt was held at this temperature for 80 minutes. Subsequently, at reduced pressure ( ⁇ 5 mbar) and a maximum internal temperature of
  • Butanediol (90.8 g, 130 mol%), succinic acid (82.4 g, 90 mol%), dimethyl terephthalate (15.0 g, 10 mol%) and glycerol 0.18 g (0.1 wt%) were dissolved in the presence of TBOT ( 0.2 g) is first heated to 200 ° C. The melt was held at this temperature for 80 minutes. Subsequently, at reduced pressure ( ⁇ 5 mbar) and a maximum internal temperature of 250 ° C., 1, 4-butanediol was distilled off. The polyester was poured out and analyzed after cooling. The polyester obtained had a viscosity number of 172 ml / g.
  • films of a thickness of about 420 ⁇ m were produced by means of a molding press.
  • iii-1 talc from Mondominerals
  • test specimens used were produced by injection molding at melt temperatures between 150 and 200 ° C and a mold temperature between room temperature and 60 ° C. Standard specimens as specified in ISO 20753 were used for the tests. The disintegration rates were determined on plates with the dimensions 60 ⁇ 60 ⁇ 1 mm 3 .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne un article fabriqué par moulage par injection contenant : i) de 50 à 85 % en poids, rapporté au poids total des composants i à ii, d'un polyester biodégradable ayant un MVR (190 °C, 2,16 kg) selon l'ISO 1133 de 10 à 100 cm3/10 min contenant : a) de 90 à 99,5 % en moles, rapporté aux composants a à b, d'acide succinique ; b) de 0,5 à 10 % en moles, rapporté aux composants a à b, d'un ou plusieurs acides dicarboxyliques en C8 à C20 ; c) de 98 à 102 % en moles, rapporté aux composants a à b, de 1,3-propane diol ou de 1,4-butane diol ; d) de 0 à 0,1 % en poids, rapporté aux composants a à c, d'un extenseur de chaîne ou d'un agent de ramification ; ii) de 5 à 50 % en poids, rapporté au poids total des composants i à ii, d'acide polylactique ; iii) de 10 à 50 % en poids, rapporté au poids total des composants i à iv, d'au moins une ou plusieurs charges minérales, au moins une charge étant de la craie ; iv) de 0 à 2 % en poids, rapporté au poids total des composants i à iv, d'un mélange de sels nutritifs contenant au moins deux composants choisis dans le groupe comprenant : un cation ou un anion contenant de l'azote, un anion contenant du soufre, un anion contenant du phosphore et un cation choisi dans le groupe comprenant K+, Na+, Ca2+, Mg2+ et Fe2/3+. La présente invention concerne en outre des procédés pour la fabrication des articles mentionnés ci-dessus.
PCT/EP2012/062321 2011-06-30 2012-06-26 Article fabriqué par moulage par injection Ceased WO2013000892A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
ES12729630.9T ES2552948T3 (es) 2011-06-30 2012-06-26 Artículo producido mediante moldeado por inyección
EP12729630.9A EP2726549B1 (fr) 2011-06-30 2012-06-26 Article fabriqué par moulage par injection
BR112013032053A BR112013032053B1 (pt) 2011-06-30 2012-06-26 artigo produzido via moldagem por injeção
CN201280031946.3A CN103635533B (zh) 2011-06-30 2012-06-26 通过注射成型制备的制品

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11172188A EP2540779A1 (fr) 2011-06-30 2011-06-30 Article fabriqué par thermoformage ou moulage par injection
EP11172188.2 2011-06-30

Publications (1)

Publication Number Publication Date
WO2013000892A1 true WO2013000892A1 (fr) 2013-01-03

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PCT/EP2012/062184 Ceased WO2013000847A1 (fr) 2011-06-30 2012-06-25 Article fabriqué par thermoformage
PCT/EP2012/062321 Ceased WO2013000892A1 (fr) 2011-06-30 2012-06-26 Article fabriqué par moulage par injection

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PCT/EP2012/062184 Ceased WO2013000847A1 (fr) 2011-06-30 2012-06-25 Article fabriqué par thermoformage

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EP (3) EP2540779A1 (fr)
CN (2) CN103649222B (fr)
BR (2) BR112013030892B1 (fr)
ES (2) ES2552926T3 (fr)
WO (2) WO2013000847A1 (fr)

Cited By (1)

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WO2020115221A1 (fr) 2018-12-06 2020-06-11 Basf Se Procédé de production d'un (co)polyester

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Publication number Priority date Publication date Assignee Title
EP2540779A1 (fr) 2011-06-30 2013-01-02 Basf Se Article fabriqué par thermoformage ou moulage par injection
AU2015257900B2 (en) 2014-05-09 2018-07-26 Basf Se Injection-moulded article
AU2015257899B2 (en) * 2014-05-09 2018-07-05 Basf Se Articles produced by thermoforming
SG11201704254XA (en) 2014-12-22 2017-07-28 Smith & Nephew Negative pressure wound therapy apparatus and methods
ES2898962T3 (es) 2019-02-15 2022-03-09 Basf Se Artículos moldeados por inyección
IT202000007963A1 (it) * 2020-04-15 2021-10-15 Novamont Spa Composizione polimerica biodegradabile per la realizzazione di articoli stampati.

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EP0488617A2 (fr) 1990-11-26 1992-06-03 Showa Highpolymer Co., Ltd. Une méthode pour la préparation de polyester saturé
WO1996015173A1 (fr) 1994-11-15 1996-05-23 Basf Aktiengesellschaft Polymeres biodegradables, leur procede de production et leur utilisation pour la fabrication de corps moules biodegradables
DE19857067A1 (de) 1997-12-15 1999-06-24 Ykk Corp Geformter Gegenstand aus biologisch abbaubarem Kunststoff
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EP2726549A1 (fr) 2014-05-07
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BR112013030892B1 (pt) 2020-04-07
EP2726549B1 (fr) 2015-08-12
CN103649222A (zh) 2014-03-19
CN103635533A (zh) 2014-03-12
CN103649222B (zh) 2015-09-16
BR112013032053A2 (pt) 2016-12-13
EP2726550B1 (fr) 2015-08-12
ES2552926T3 (es) 2015-12-03
ES2552948T3 (es) 2015-12-03
BR112013032053B1 (pt) 2020-04-07
EP2726550A1 (fr) 2014-05-07
CN103635533B (zh) 2015-07-15
EP2540779A1 (fr) 2013-01-02

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